2,4-Dimethyl-2-penten-3-yl-triflate | 52149-35-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 2,4-Dimethyl-2-penten-3-yl-triflate
• 英文别名: 2,4-dimethylpent-2-en-3-yl trifluoromethanesulfonate
• CAS: 52149-35-6
• 化学式: C₈H₁₃F₃O₃S
• 分子量: 246.251
• InChiKey: CKUMUAJMLDRDAS-UHFFFAOYSA-N

物化性质

• 沸点：
  239.2±40.0 °C(Predicted)
• 密度：
  1.243±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  2,4-Dimethyl-2-penten-3-yl-triflate 在 吡啶 、 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 sodium hexamethyldisilazane 、 sodium hydroxide 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 20.75h， 生成 1-(2-(2,4-dimethylpent-2-en-3-yl)phenyl)-1-methyl-3-(2,3,4,5-tetrafluorophenyl)urea
  参考文献：
  名称：

  通过脱氢[3 + 2]电化学合成（Aza）二氢吲哚：在（±）-Hinckdentine A的全合成中的应用

  摘要：

  已经开发了通过芳胺与链状烯烃的脱氢[3 + 2]环合进行官能化（氮杂）二氢吲哚的电化学合成方法。先前报道的通过类似的分子间和分子内环化反应进行的合成需要贵金属催化剂，并且大多限于末端烯烃或1,3-二烯。电合成采用容易获得且便宜的二茂铁作为分子催化剂，并与二，三，甚至四取代的烯烃相容，以构建二氢吲哚以及更具挑战性的氮杂二氢吲哚。利用新开发的电合成作为关键步骤，已从市售材料中分12个步骤（最长的线性序列）完成了海洋生物碱（±）-扁桃碱A的全合成。

  DOI：

  10.1002/cjoc.201800301
• 作为产物：
  描述：

  N-苯基双(三氟甲烷磺酰)亚胺 、 2,4-二甲基-3-戊酮 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 2,4-Dimethyl-2-penten-3-yl-triflate
  参考文献：
  名称：

  Further demonstration of the higher reactivity of the vinyl hydrogen rather than the allyl hydrogen towards singlet oxygen

  摘要：

  在一种新的线性扭曲的1,3-二烯中，观察到乙烯氢相对于仲烯氢对单态氧的异常高反应性。

  DOI：

  10.1039/a705924h

文献信息

• Palladium-Catalyzed Visible-Light-Driven Carboxylation of Aryl and Alkenyl Triflates by Using Photoredox Catalysts
  作者：Katsuya Shimomaki、Tomoya Nakajima、Joaquim Caner、Naoyuki Toriumi、Nobuharu Iwasawa

  DOI：10.1021/acs.orglett.9b01340

  日期：2019.6.21

  A visible-light-driven carboxylation of aryl and alkenyl triflates with CO2 is developed by using a combination of Pd and photoredox catalysts. This reaction proceeds under mild conditions and can be applied to a wide range of substrates including acyclic alkenyl triflates.

  通过使用Pd和光氧化还原催化剂的组合，可见光驱动的芳基和烯基三氟甲磺酸酯与CO 2的羧化反应。该反应在温和的条件下进行，可用于多种底物，包括无环烯基三氟甲磺酸酯。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: F: PerFHalOrg.SVol.3, 6.2.3.1, page 48 - 120
  作者：

  DOI：——

  日期：——
• Solvolysis of vinyl triflates. Effect of alkyl substituents, solvents, and added nucleophiles
  作者：Richard H. Summerville、Carol A. Senkler、Paul Von R. Schleyer

  DOI：10.1021/ja00811a026

  日期：1974.2
• Vinyl triflates in synthesis. II. 1,1-Di-, tri-, tetrasubstituted and deuterio allenes from ketones via vinyl triflates
  作者：Peter J. Stang、Robert J. Hargrove

  DOI：10.1021/jo00893a026

  日期：1975.3
• Photosensitized Oxygenation of Twisted 1,3-Dienes:  Abnormally Higher Reactivity of Vinyl Hydrogen Rather than Allyl Hydrogen toward Singlet Oxygen
  作者：Hajime Mori、Keiichi Ikoma、Sachihiko Isoe、Kazuo Kitaura、Shigeo Katsumura

  DOI：10.1021/jo980955o

  日期：1998.11.1

  As one of the novel examples to investigate the characteristic reactivity of significantly twisted 1,3-dienes, the photosensitized oxygenation of two types of significantly twisted 1,3-dienes, cis-beta-ionol derivative 2 and acyclic derivative Il, is investigated. Photosensitized oxygenation of 2a-f and 11a-e revealed that the vinyl hydrogen Ha was more reactive than the allyl hydrogen Hb. Thus, phenyl derivative 2e and tert-butyl-substituted compound lid selectively produced allenes 3e and 13d in 67% and 75% yield resulting from the ene reaction of the vinyl hydrogen Ha rather than allyl alcohols 4e and 14d resulting from the allyl hydrogen abstraction in 24% and 8% yield, respectively. Furthermore, in the case of methyl-substituted compound 11b, the extent of the inherent reactivity of the vinyl hydrogen Ha was similar to that of the allyl hydrogen He. On the basis of X-ray analysis and NIM and MO calculations, the discovered abnormally higher reactivity of the vinyl hydrogen would be rationalized by considering mainly the large sigma*-pi orbital interaction between the vinyl C-H bond and another double bond in significantly twisted 1,3-dienes resulting from calculations of HOMO electron densities.